CN1325369C - Process for producing synthetic gas with heavy raw materials such as heavy crude oil an distillation residues through partial oxidation - Google Patents

Process for producing synthetic gas with heavy raw materials such as heavy crude oil an distillation residues through partial oxidation Download PDF

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Publication number
CN1325369C
CN1325369C CNB03133086XA CN03133086A CN1325369C CN 1325369 C CN1325369 C CN 1325369C CN B03133086X A CNB03133086X A CN B03133086XA CN 03133086 A CN03133086 A CN 03133086A CN 1325369 C CN1325369 C CN 1325369C
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synthetic gas
heavy
gas
concentric tube
adduction pipe
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CN1486924A (en
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多梅尼科·圣菲利波
伊万诺·米拉卡
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Snamprogetti Joint Stock Co Ltd
SnamProgetti SpA
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Snamprogetti Joint Stock Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0006—Controlling or regulating processes
    • B01J19/0013—Controlling the temperature of the process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/06—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials combined with spraying with water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00121—Controlling the temperature by direct heating or cooling
    • B01J2219/00123—Controlling the temperature by direct heating or cooling adding a temperature modifying medium to the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00243—Mathematical modelling

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Industrial Gases (AREA)

Abstract

Process for the production of synthesis gas from heavy charges comprising a partial oxidation of heavy charges with oxygen or air enriched in oxygen in the presence of vapour, carried out at temperatures higher than 1000 DEG C. and pressures equal to or higher than 20 atm and the subsequent cooling of the synthesis gas obtained, by the direct injection of water into the gas itself followed by the separation of the water effected by means of an adduction pipe surrounded by a concentric tube open at both ends so as to form a ring through which the cooled gas and water can rise, characterized in that the distance (L) between the lower end of the adduction pipe and the lower end of the open concentric tube must be equal to or higher than x times the diameter (D) of said lower end of the adduction pipe, wherein x varies in relation to the specific gas mass flow-rate (F), expressed in kg/h/cm<2>, according to the equation x=0.026 F+0.15.

Description

The method of using the heavy feed stock such as heavy crude and distillation residue to produce synthetic gas by partial oxidation
Technical field
The method that the present invention relates to use the pitch that extracts such as heavy crude, from oil-sand and the heavy feed stock the distillation residue to produce synthetic gas by partial oxidation.
Background technology
Pitch that extracts heavy crude, from oil-sand and petroleum residue are converted into high-quality product roughly can two kinds of methods: the one, add thermosetting intermediates synthetic gas separately; The 2nd, pass through hydrogen treatment.
With regard to independent heating method, heavy feed stock and oxygen and the combustion moderator such as steam are heated to high temperature (more than 1000 degrees centigrade) together produce synthetic gas, this has been well-known.
All reactions at high temperature all reach balance, the H that obtains 2/ CO mole ratio generally all can make CO concentration keep very highly, CO 2Generation seldom, no matter be to be used for chemical aspect, still be used for suitable combined cycle system combustion power generation, carbon monoxide all is a carbon burning product of forming this synthetic gas.
This gas that generates under high-temperature very must cool off, and reclaiming contained heat, and makes it to obtain to handle, to remove as metal particle contained in the heavy feed stock, hydrogen sulfide and other compounds.
Cooling can be implemented by the way of carrying out heat exchange with suitable surface, thereby or implements to help separating particles or oil smoke (carbon particulate of the imperfect combustion formation of heavy feed stock of adding) with the method for water filling.
Successively existing in this respect many patents are wherein mentioned US 2828326, US3980950, US 4605423, US 4705542 and US 4704137 especially.
Can from these patents, notice understanding and keep H as far as possible 2How important/CO mole ratio is constant is; This has also caused serious problems, because described ratio is approximately less than 1, but the tendency that rises to greater than 1 is arranged, the obviously later use of this gas of influence.
US 2818326 has illustrated a kind of method of producing synthetic gas.This method is exactly to produce synthetic gas with carbonaceous fuel with the oxygen-containing gas partial oxidation, then with the direct synthetic gas that is obtained to the method cooling of wherein water filling, then again moisture is left, isolating method is with the adduction pipe that is wrapping the concentric tube of both ends open on every side, thereby form an annulus, the refrigerative G﹠W can pass this annulus and rise.This patent also ad hoc proposal is cooled to 600_ to the hot gas of discharging from 2000_ in a short period of time, with the DeR that prevents from generally to cause uncombined carbon and hydrocarbon polymer to generate, but the time that do not specify to be short to which kind of degree.
US 4705542 comprises the explanation to above-identified patent, and the suggestion operating rate is the 2--9 meter per second, and cooling was carried out with the duration of contact of 0.1-1 second, and preferred version is 0.1-0.5 second.
Although two top patents are described, though cooling is to add liquid water and to carry out in the of short duration cooling time of suggestion, can find to be not sufficient to guarantee that this method can correctly work.
As everyone knows, in fact, except DeR above-mentioned, wherein have Bouduart reaction 2CO ← → C+CO 2(△ H °=-173kj/mole), this reaction has the shortcoming that forms the carbonaceous solids particulate, helps water gas shift reaction CO+H and add water 2O (g) ← → CO 2+ H 2(△ H °=-41.115kj/mole).
Reach water gas shift reaction slowly to being enough to have required about 900 ℃ time of selection as much as possible crucial especially.
As thermodynamic (al) result, this reaction is tending towards to the right owing to temperature is more and more lower.
The synthetic gas of Huo Deing has lower thermal power like this, and hydrogen richness is higher, and carbon monoxide content is lower, and gas concentration lwevel improves.
Do not having effectively to cool off under the situation of the composition of controlling synthetic gas, must be with still less some steam enforcement gasifications.
Everything causes various shortcomings, and wherein most important have:
-generation oil smoke;
-lost heat capacity owing to the water gas shift reaction and the oil smoke of removing generation (this also is dangerous refuse) of heating;
-having and corrode and/or corrosion, this causes using more expensive material.
All these shortcomings all can cause the work interruption.
Yet, with the method for direct water filling cooling and subsidiary when removing oil smoke, having found rises to gush at synthetic gas forms the high temperature bubble in the equipment of liquid below passing, it is not good to distribute in liquid, thereby can expection can cause that equipment work is undesired and (spume, horizontal plane is uneven, carries synthetic gas in the liquid water secretly, and synthetic gas is brought into liquid phase).
Also reduce the foam that under the high turbulent-flow conditions of whole isolated water, produces simultaneously for fear of above-mentioned shortcoming, we have found that the lower end of described adduction pipe and the distance between the described concentric tube lower end must be equal to or higher than certain value, described certain value is decided by the diameter of adduction pipe lower end and the concrete flow velocity of synthetic gas, thereby prevents that the synthetic gas that sprays from passing the lower end of the concentric tube that surpasses described opening.
Summary of the invention
The method with heavy feed stock production synthetic gas as the object of the invention comprises: described heavy feed stock and oxygen or rich oxygen containing air are having steam, and temperature is higher than 1000 ℃, and pressure is preferably in and is equal to or higher than 20 atmospheric situation lower section oxidations; With direct way to wherein water filling obtained synthetic gas cooled off thereafter, then again moisture is left, isolating method is to wrap the adduction pipe of the concentric tube of both ends open around using, thereby forms an annulus, and cooled synthetic G﹠W can pass described annulus and rise.It is characterized in that x that distance L between the concentric tube lower end of the lower end of adduction pipe and opening must be equal to or greater than described adduction pipe lower end diameter doubly, described x changes with the concrete flow rate F of synthetic gas, with kilogram/hour/centimetre 2Expression can be calculated according to following formula: x=0.026F+0.15.
The heavy feed stock of handling can have various sources: can be selected from heavy crude, distillation residue, from the heavy oil of catalytic treatment, for example come heavy recycle stock that catalytic cracking handles, thermal tar (for example from viscosity breaking or similar hot procedure), the pitch from oil-sand, various coal and industry to be commonly considered as the raw material of other higher boiling point hydrocarbon compound properties of " dirty oil ".
Description of drawings
The preferred embodiment of band accompanying drawing of the present invention is provided below, yet, should think that never it limits the scope of the invention.
Fig. 1 illustrates the synoptic diagram of one embodiment of the present of invention
Embodiment
Fig. 1 is the synoptic diagram of embodiment, wherein, the cooling of the carbonaceous particles synthetic gas of obtaining from the heavy feed stock partial oxidation 1 is to carry out with the way of direct water filling 2 among synthetic gas, then in proper container R, the moisture that injects is left, its method is the adduction pipe TA that the concentric tube TC with a velamen both ends open is wrapping, thereby form an annulus, the synthetic G﹠W of refrigerative can pass described annulus and rise.
Distance L between the concentric tube lower end of adduction pipe lower end and opening must be equal to or greater than x times of described adduction pipe lower end diameter, and wherein x changes with the concrete flow rate F of synthetic gas, the unit kilogram/hour/centimetre 2Expression can be calculated according to following formula: x=0.026F+0.15.
Water is removed from the bottom 3 of described container with carbonaceous particles, and the refrigerative synthetic gas is then discharged from the point 4 of side.
Several examples are provided below, but should think that never these examples limit the scope of the invention.
Example 1
Partial oxidation is heavy feed stock 30t/h and the oxygen 31t/h that comprises the bituminous matter residue with inlet amount, 1350 ℃ of temperature, is added with under the situation of pressure 72atm under the condition of steam 19t/h and carries out, and obtains synthetic gas 96200Nm 3/ h, described synthetic gas are with the way cooling of directly water filling in it, and the water section vaporization of injection is brought up to 117500Nm to the gas phase flow velocity 3/ h then, separates liquid water according to the arrangement of accompanying drawing, and the diameter D of adduction pipe lower end is 0.8m.
Because flow rate F=18.79kg/h/cm 2, the value of x is 0.64, so described distance L must be equal to or greater than 0.51m.
After selecting described distance L=0.55m, can see the working properly of system, there is not problem foamy, there is not bubble formation adjusting level in other words to have no problem in the whole liquid outside the described concentric tube, proof is all round intra-annular risings between described adduction pipe and concentric tube of gas phase almost, do not influence the container that comprises liquid phase.
Example 2
Partial oxidation is heavy feed stock 30t/h and the oxygen 31t/h that comprises the bituminous matter residue with inlet amount, 1350 ℃ of temperature, is added with under the situation of pressure 72atm under the condition of steam 19t/h and carries out, and obtains synthetic gas 96200Nm 3/ h, described synthetic gas are with the way cooling of directly water filling in it, and the water section vaporization of injection is brought up to 117500Nm to the gas phase flow velocity 3/ h then, separates liquid water according to the arrangement of accompanying drawing, and the diameter D of adduction pipe lower end is 0.6m.
Because flow rate F=33.40kg/h/cm 2, the value of x is 1.02, so described distance L must be equal to or greater than 0.61m.
After selecting described distance L=0.65m, can see the working properly of system, there is not problem foamy, there is not bubble formation adjusting level in other words to have no problem in the whole liquid outside the described concentric tube, proof almost all gas phases all be to rise in the annulus between described adduction pipe and concentric tube, do not influence the container that comprises liquid phase.
Example 3 (comparison)
Partial oxidation is heavy feed stock 30t/h and the oxygen 31t/h that comprises the bituminous matter residue with inlet amount, 1350 ℃ of temperature, is added with under the situation of pressure 72atm under the condition of steam 19t/h and carries out, and obtains synthetic gas 96200Nm 3/ h, described synthetic gas are with the way cooling of directly water filling in it, and the water section vaporization of injection is brought up to 117500Nm to the gas phase flow velocity 3/ h then, separates liquid water according to the arrangement of accompanying drawing, and the diameter D of adduction pipe lower end is 0.8m.
With described distance L=0.45m, can see that the work of system is undesired, be difficult to the adjusting level in the described container, reason is to have gas phase, its form is an air pocket, and described bubble rises in the outer liquid phase of concentric tube, rather than enters in the annulus between adduction pipe and the concentric tube.

Claims (1)

1. method of producing synthetic gas with heavy feed stock, described method comprises: the air of heavy feed stock and oxygen or oxygen enrichment is having steam, and temperature is higher than 1000 ℃, and pressure is equal to or higher than 20 atmospheric situation lower section oxidations; With direct way to wherein water filling obtained synthetic gas cooled off thereafter, then again moisture is left, its method is the adduction pipe that the concentric tube with both ends open is wrapping, thereby form an annulus, cooled synthetic G﹠W can pass described annulus and rise, the feature of described method be the distance L between the concentric tube lower end of adduction pipe lower end and opening be equal to or greater than described adduction pipe lower end diameter x doubly, wherein x changes with the concrete flow rate F of synthetic gas, unit is with kilogram/hour/centimetre 2Expression is calculated according to following formula: x=0.026F+0.15.
CNB03133086XA 2002-07-26 2003-07-25 Process for producing synthetic gas with heavy raw materials such as heavy crude oil an distillation residues through partial oxidation Expired - Fee Related CN1325369C (en)

Applications Claiming Priority (2)

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IT001663A/2002 2002-07-26
IT2002MI001663A ITMI20021663A1 (en) 2002-07-26 2002-07-26 PROCEDURE FOR THE PRODUCTION OF SYNTHESIS GAS FROM HEAVY CHARGES SUCH AS HEAVY OILS AND DISTILLATION RESIDUES USING OXIDATION

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CN1486924A CN1486924A (en) 2004-04-07
CN1325369C true CN1325369C (en) 2007-07-11

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US (1) US7163647B2 (en)
EP (1) EP1384699B1 (en)
JP (1) JP4434645B2 (en)
CN (1) CN1325369C (en)
AT (1) ATE293086T1 (en)
DE (1) DE60300499T2 (en)
DK (1) DK1384699T3 (en)
ES (1) ES2237735T3 (en)
IT (1) ITMI20021663A1 (en)

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Publication number Priority date Publication date Assignee Title
US7621973B2 (en) 2005-12-15 2009-11-24 General Electric Company Methods and systems for partial moderator bypass
US20080000155A1 (en) * 2006-05-01 2008-01-03 Van Den Berg Robert E Gasification system and its use
CN101432400B (en) 2006-05-01 2012-11-14 国际壳牌研究有限公司 Gasification reactor and its use
US9051522B2 (en) * 2006-12-01 2015-06-09 Shell Oil Company Gasification reactor
US8960651B2 (en) * 2008-12-04 2015-02-24 Shell Oil Company Vessel for cooling syngas

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704137A (en) * 1987-02-09 1987-11-03 Texaco Inc. Process for upgrading water used in cooling and cleaning of raw synthesis gas
CN1077175A (en) * 1993-02-02 1993-10-13 中国五环化学工程公司 Ammonia-preparing technique from heavy oil

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2818326A (en) * 1956-08-07 1957-12-31 Texas Co Method of shutting down the gas generator
US4605423A (en) * 1982-04-12 1986-08-12 Texaco Development Corporation Apparatus for generating and cooling synthesis gas
US4705542A (en) * 1984-03-01 1987-11-10 Texaco Inc. Production of synthesis gas
IT1317722B1 (en) * 2000-01-13 2003-07-15 Snam Progetti PROCEDURE FOR THE PRODUCTION OF SYNTHESIS GAS.
US6656387B2 (en) * 2001-09-10 2003-12-02 Texaco Inc. Ammonia injection for minimizing waste water treatment

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4704137A (en) * 1987-02-09 1987-11-03 Texaco Inc. Process for upgrading water used in cooling and cleaning of raw synthesis gas
EP0278063A2 (en) * 1987-02-09 1988-08-17 Texaco Development Corporation Process for upgrading water used in cooling and cleaning of raw synthesis gas
DE3784692D1 (en) * 1987-02-09 1993-04-15 Texaco Development Corp METHOD FOR IMPROVING THE QUALITY OF WATER APPLIED FOR COOLING AND WASHING AN UNPURED SYNTHESIS GAS.
CN1077175A (en) * 1993-02-02 1993-10-13 中国五环化学工程公司 Ammonia-preparing technique from heavy oil

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JP2005002306A (en) 2005-01-06
DK1384699T3 (en) 2005-06-27
CN1486924A (en) 2004-04-07
EP1384699B1 (en) 2005-04-13
ITMI20021663A1 (en) 2004-01-26
DE60300499T2 (en) 2006-02-23
EP1384699A1 (en) 2004-01-28
US7163647B2 (en) 2007-01-16
JP4434645B2 (en) 2010-03-17
ATE293086T1 (en) 2005-04-15
DE60300499D1 (en) 2005-05-19
US20050074395A1 (en) 2005-04-07
ES2237735T3 (en) 2005-08-01

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